Solubilized 8-hydroxyquinoline and method of producing same



United States Patent SOLUBIILIZED 8-HYDROXYQUINOLINE AND METHUD 0F PRODUCING SAME Albright M. Nicholson, Warrensville, and Stanley B. Elliott, Shaker Heights, Ghio, assignors to Ferro Corporation, Cleveland, Ohio, a corporation No Drawing. Application August 25, 1952, Serial No. 306,292

12 Claims. (Cl. 260--27i)) The present invention is a continuation-in-part of our present application Serial Number 257,944, filed November 23, 1951, now abandoned.

This invention relates as indicated to compositions having fungicidal and/or fungistatic properties and has more particular reference to a process for solubilizing such compositions.

During the past decade considerable research has been conducted for the purpose of finding new and improved fungicidal compositions. It is well known that the hydroxyquinolines have good fungicidal and/or fungistatic properties. However, they are all substantially insoluble in all of the common industrial solvents and therefore have encountered considerable ditficulties in commercial applications. Since these above mentioned materials are so extremely difficult to incorporate into fungicidal compositions they have poor resistance to crocking and leaching and lose their effectiveness due to poor penetration of the material being treated.

It is therefore a principal object of our invention to provide a method and means for rendering the hydroxyquinolines soluble in the common industrial solvents such as toluene, V. M. and P. naphtha, mineral spirits, fuel oil etc.

Other objects will become apparent as the description proceeds.

To the accomplishment of the foregoing and related ends, the invention, then, comprises the features hereinafter fully described and particularly pointed out in the claims, the following description setting forth in detail certain illustrative embodiments of the invention, these being indicative, however, of but a few of the various ways in which the principle of the invention may be employed.

Broadly stated this invention comprises the process of solubilizing the hydroxyquinolines which consists in heating a hydroxyquinoline with a material selected from the class consisting of water insoluble metal carboxylic acid soaps, water insoluble metal alkyl phenylates in which the alkyl group has at least 8 and not more than carbon atoms, water insoluble metal alkyl phosphates in which the alkyl group has at least 3 and not more than 12 carbon atoms, admixtures of water insoluble metal carboxylic acid soaps and water insoluble metal alkyl phenylates in which the alkyl group has at least 8 and not more than 15 carbon atoms and admixtures ofwater insoluble metal carboxylic acid soaps and water insoluble metal alkyl phosphates in which the alkyl group has at least 3 and not more than 12 carbon atoms.

The alkyl radicals of the phenylates and phosphates, used as reactants in the present invention, may be normal or branched. In the case of dialkyl compounds the two alkyl radicals are not necessarily similar. The phenylates and phosphates may be salts of any metal which metal forms a water-insoluble compound with the alkyl phenylates and phosphates. We have found the copper, zinc and nickel salts of the following alkyl compounds to be particularly useful in the process of our invention:

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Butyl phosphoric acid Amyl phosphoric acid Iso-octyl phosphoric acid Monyl phosphoric acid Dodecyl phosphoric acid Octyl phenol Monyl phenol Dodecyl phenol Penta-decyl phenol The metal soaps which are used as reactants in the present invention are the water insoluble soaps. Thus they may be soaps of any metal or mixture of metals which form water insoluble soaps with soap-forming acids or mixtures of such acids. In the preferred embodiment of our invention we use the copper, zinc and nickel soaps.

The soap-forming acids used in forming the aforementioned metal soaps include stearic, palmitic, lauric, 2 ethyl-hexoic, linoleic, linolenic, oleic ricinoleic, and naphthenic and mixtures thereof. Other soap-forming fatty acids such as tall oil rosin oil, rosin and abietic may also be used in making the above mentioned waterinsoluble soaps. In the preferred embodiment of our invention we use those saturated and unsaturated aliphatic acids having from eight to eighteen carbon atoms.

As previously indicated the hydroxyquinolines are substantially insoluble in the common organic solvents, the reaction products of the present invention, on the other hand, are readily soluble in toluene, mineral spirits, naphtha, fuel oil, etc. and the resultant solutions have very effective fungicidal properties.

While the hydroxyquinolines in general are effective as fungicides we prefer the use of S-hydroxyquinoline in our present invention. We have also found that the solubilized reaction products of the present process have substantially higher fungicidal activity than the hydroxyquinolines by themselves.

We have found that in order to effect good solubilization of 8-hydroxyquinoline in any of the aforementioned compounds the mixture of the reactants should be heated to a temperature in the range of about 200 F. to the lowest decomposition temperature of the components, with good agitation.

From about 5% to about 20% of 8-hydroxyquinoline can be substantially completely put into solution in the above discussed compounds.

The following examples are illustrative of a few ways of preparing the reaction products of the present invention.

In carrying out the process of the present invention it was found that the reactions would more readily go to completion in the presence of a reaction medium. By reaction medium is meant the presence of free acid. In other words if a naphthenate soap is used the reaction would contain an excess of free naphthenic acid, or if a metal alkyl phenylate is used, the reaction would contain an excess of free phenol etc.

Example I 83.5 parts by weight of copper naphthenate (11.0% copper content) were heated with 16.5 parts by weight of 8-hydroxyquinoline in an open vessel, with constant agitation, to 375 F. The temperature was held for about 45 minutes, The solution was allowed to cool to about F. and was then diluted to about 18.5% with mineral spirits.

The resulting solution was brilliant, clear and free from undissolved matter when observed by the eye under a light.

The reaction products of the present invention at room temperature vary from free flowing masses to solids. However, all are readily soluble and may be diluted with any of the common solvents such as mineral spirits, as

shown above. Generally the reaction products of the present invention can be diluted with the common organic solvents at room temperature, however, we have found that the use of heat will usually facilitate dispersion.

The products of the present invention may be applied in the material to be treated by dipping, spraying or by being incorporated into a still more complex composition and then knifed onto the material. The aforementioned complex compositions maybe any of a wide variety of resins and various water-proofing agents.

Example II 33 parts by weight of copper naphthenate (11.0% copper content) were heated with 17 parts by weight of 8- hydroxyquinoline and 50 parts by weight of nickel naphthenate in an open vessel. The mixture was heated to 350 F. with constant agitation for about 20 minutes. The resultant reaction product was readily soluble in any of the common organic solvents.

The reaction products of the present invention may be used as fungicidal and/or fungistatic compositions in the hot liquified state or in the solidified state or as hot or cold solutions in the common organic solvents.

Example III 28 parts by weight of copper mono and di-iso-octyl phosphate were heated with 56 parts by weight of mono and di-iso-octyl phosphoric acid to about 200 F. in an open vessel and then 16.4 parts by weight of S-hydroxyquinoline were stirred in and the temperature was raised to 325 F. and held for about 25 minutes with constant agitation.

The resultant reaction product when diluted in mineral spirits showed exceptionally good clarity and no undissolved matter when observed under light.

Example IV 36 parts by weight of copper mono and di-amyl phos phate were heated in an open vessel with 40 parts by weight of mono and di-amyl phosphoric acid to about 200 F. and then 24.6 parts by weight of 8-hydroxyquinoline the temperature was raised to 325 F. and held for about 25 minutes with constant agitation.

The resultant product was readily soluble in any of the aforementioned solvents and showed excellent fungicidal properties.

Example V 91.7 parts by weight of nickel octyl phenylate were heated in an open vessel with 8.3 parts by weight of 8- hydroxyquinoline to 350 F. for about 30 minutes with constant agitation.

The resultant product had excellent fungistatic properties.

Example VI 31.8 parts by weight of copper mono and di-iso-octyl phosphate, 60 parts by weight of nickel mono and di-isooctyl phosphate and 8.2 parts by weight of 8-hydroxyquinoline were heated in an open vessel to 350 F. for about 20 minutes with constant agitation.

The resultant product was a free flowing mass which was readily soluble in the common organic solvents.

Example VII 73.9 parts by weight of copper mono and di-amyl phosphate were heated with 17.9 parts by weight of mono and di-amyl phosphoric acid and 8.2 parts by weight of 8- hydroxyquinoline in an open vessel to 350 F. for about 20 minutes with constant agitation.

The resultant product was a free flowing mass which was readily soluble in the common organic solvents.

Example VIII 91.7 parts by weight of nickel octyl phenylate were heated with 41.3 parts by weight of nickel naphthenate in an open vessel to about 200 F. with agitation for about 20 minutes and then 16.6 parts by weight of 8-hydroxyquinoline were added and the temperature was raised to about 325 F. and held for about 25 minutes with constant agitation.

The resultant product when diluted in mineral spirits showed good clarity and no undissolved matter when viewed under light.

Example IX 54.0 parts by weight of a copper salt of mono and diamyl phosphoric acid were heated in an open vessel with 41.7 parts by weight of copper naphthenate to about 200 F. with agitation for about 20 minutes and then 16.6 parts by weight of 8-hydroxyquinoline Were stirred in and the temperature raised to about 325 F. and held for about 25 minutes with constant agitation.

The resultant product had excellent clarity and very good fungicidal properties.

Example X 91.7 parts by weight of nickel actyl phenylate and 27.0 parts by weight of a nickel salt of mono and di amylphosphoric acid were heated together in an open vessel with agitation to 200 F. for about 20 minutes. 16.6 parts by weight of 8-hydroxyquinoline were then stirred in and the temperature raised to about 325 F. and held for about 25 minutes with constant agitation.

The resultant product readily dispersed in mineral spirits and showed excellent fungistatic properties.

Tests were carried out on the products of the present invention to determine their efficacy as fungicides. The tests were as follows:

Samples of 10 oz. duck were cut 1%" X 6" and the width was ravelled to 1". Half of the samples were cut parallel 'to the warp threads and the other half of the samples were cut parallel to the filling threads. Untreated specimens were always included in the tests as controls to verify the viability of the test organisms.

The samples to be treated were dipped into a solution of one of the products of the present invention. As for example, the reaction product of Example I was diluted to 18.5 with mineral spirits and the textiles to be treated were dipped into this solution for 1 minute. The treated textiles were then put through a wringer and adjusted to a 65% pick up of the fungicide on a dry Weight basis, and they were then allowed to air dry to constant weight. One-half of the treated samples were placed directly in the fungus growth and the other half of the treated samples were thoroughly leached in water and dried before being subjected to the fungus growth.

Spore suspensions of Chaetomium globosum and Aspergillus nz'ger were introduced onto an agar culture medium contained in a sterile bottle, and then incubated for 48 hours at 84 i 2 F. at -95% relative humidity. At the end of the 48 hour incubation period the treated textile samples (leached and unleached) and the untreated textile samples were dipped in distilled water and then pressed firmly on the surface of the inoculated culture medium to insure good contact. After 14 days the samples were observed visually and subjected to breaking tests.

At the end of 14 days all untreated samples were completely covered by fungi growth and were reduced in tensile strength by 50% or more. The treated samples both leached and unleached showed no fungus growth r and substantially on loss in tensile strength. There was no difference in appearance between the leached and unleached treated samples, however the leached samples showed a slightly higher tensile strength than did the unleached samples.

The present invention is not to be construed as limited to the details of Example I. Additional reaction products of the present invention were used to determine their efficacy as fungicides. Solutions of each of these products were used to impregnate samples of duck and they showed results substantially identical with the results above discu ed.

The products of the present invention are stable for long periods of time and not only inhibit the growth of fungi but may also kill the activity of existing growth on contact.

Other modes of applying the principle of the invention may be employed, change being made as regards the details described, provided the feature stated in any of the following claims or the equivalent of such be employed.

We, therefore, particularly point out and distinctly claim as our invention:

1. The method of producing a composition of matter which consists of reacting at temperatures between 200 F. and the lowest decomposition temperature of the reactants, 8-hydroxyquinoline, with at least one water insoluble metal organic acid soap, said metal soap se lected from the group consisting of the metal water insoluble soaps of stearic, palmitic, lauric, 2-ethyl-hexoic, linoleic, linolenic, oleic, ricinoleic, naphthenic, tall oil, rosin oil, rosin and abetic acids.

2. The method of producing a composition of matter which consists of reacting at temperatures between 200 F. and the lowest decomposition temperature of the reactants, 8-hydroxyquinoline, with at least one water insoluble metal organic acid soap, said metal soap selected from the group consisting of the metal water insoluble soaps of stearic, palmitic, lauric, 2-ethyl-hexoic, linoleic, linolenic, oleic, ricinoleic, naphthenic, tall oil, rosin oil, rosin and abetic acids.

3. A method of producing a composition of matter which consists of reacting at temperatures between 200 F. and the lowest decomposition temperature of the reactants, S-hydroxyquinoline and copper naphthenate.

4. A method of producing a composition of matter which consists of reacting at temperatures between 200 F. and the lowest decomposition temperature of the reactants, S-hydroxyquinoline and copper laurate.

5. A method of producing a composition of matter which consists of reacting at temperatures between 200 F. and the lowest decomposition temperature of the reactants, 8-hydroxyquinoline and nickel Z-ethylene hexoate.

6. A method of producing a composition of matter which consists of reacting at temperatures between 200 F. and the lowest decomposition temperature of the reactants, S-hydroxyquinoline and zinc laurate.

7. As a new composition of matter the product produced by claim 1.

8. As a new composition of matter the product produced by claim 2.

9. As a new composition of matter the product produced by claim 3.

10. As a new composition of matter the product produced by claim 4.

11. As a new composition of matter the product produced by claim 5.

12. As a new composition of matter the product produced by claim 6.

References Cited in the file of this patent UNITED STATES PATENTS 2,085,065 Andersen June 29, 1937 2,371,691 Hawkinson et al .1 Mar. 20, 1945 2,381,863 Benignus 1 Aug. 14, 1945 2,387,591 Kolb Oct. 23, 1945 2,561,379 Kalberg July 24, 1951 2,561,380 Kalberg July 24, 1951 OTHER REFERENCES Rigler et al.: Ind. and Eng. Chem, vol. 33, pp. 693-4 Nakatsuka, Chem. Abstr., vol. 30, cols. 4115-6 (1936). 

1. THE METHOD OF PRODUCING A COMPOSITION OF MATTER WHICH CONSISTS OF REACTING AT TEMPERATURES BETWEEN 200* F. AND THE LOWEST DECOMPOSITION TEMPERATURE OF THE REACTANTS, 8-HYDROXYQUINOLINE, WITH AT LEAST ONE WATER INSOLUBLE METAL ORGANIC ACID SOAP, SAID METAL SOAP SELECTED FROM THE GROUP CONSISTING OF THE METAL WATER INSOLUBLE SOAPS OF STEARIC, PALMITIC, LAURIC, 2-ETHYL-HEXOIC, LINOLEIC, LINOLENIC, OLEIC, RICINOLEIC, NAPHTHENIC TALL OIL, ROSIN OIL ROSIN AND ABETIC ACIDS.
 7. AS A NEW COMPOSITION OF MATTER THE PRODUCT PRODUCED BY CLAIM
 1. 